EP0390908A1 - MELANGES DE POLYMERES DE CRISTAL LIQUIDE, D'HYDROQUINONE, DE POLYMERES POLY(ISO-TEREPHTHALATES) D'ACIDE p-HYDROXYBENZOIQUE ET D'AUTRES POLYMERES DE CRISTAL LIQUIDE CONTENANT DES DERIVES - Google Patents

MELANGES DE POLYMERES DE CRISTAL LIQUIDE, D'HYDROQUINONE, DE POLYMERES POLY(ISO-TEREPHTHALATES) D'ACIDE p-HYDROXYBENZOIQUE ET D'AUTRES POLYMERES DE CRISTAL LIQUIDE CONTENANT DES DERIVES

Info

Publication number
EP0390908A1
EP0390908A1 EP89911917A EP89911917A EP0390908A1 EP 0390908 A1 EP0390908 A1 EP 0390908A1 EP 89911917 A EP89911917 A EP 89911917A EP 89911917 A EP89911917 A EP 89911917A EP 0390908 A1 EP0390908 A1 EP 0390908A1
Authority
EP
European Patent Office
Prior art keywords
polyester
lcp
units
alloy
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP89911917A
Other languages
German (de)
English (en)
Other versions
EP0390908A4 (en
Inventor
Paul Joseph Huspeni
Brian Allen Stern
Paul David Frayer
Richard Layton
Markus Matzner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP Corp North America Inc
Original Assignee
BP Corp North America Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BP Corp North America Inc filed Critical BP Corp North America Inc
Publication of EP0390908A1 publication Critical patent/EP0390908A1/fr
Publication of EP0390908A4 publication Critical patent/EP0390908A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • This invention relates to a blend comprising a first LCP polyester polymer consisting essentially of units (I), (ll), (llI), and (IV).
  • a second LCP polyester polymer comprising at least one moiety selected from the group consisting of hydroxybenzoic acid, hydroxynaphthalene carboxylic acid, dihydroxy naphthalene, naphthalene dicarboxylic acid, oxybisbenzoic acid and substituted hydroquinones wherein the said moiety or moieties comprised) at least about 5 mole percent of the units in said second LCP polyester.
  • the homopolymer of p-hydroxybenzoic acid is a very high melting, insoluble material and, hence, very difficult to fabricate. Melting points as high as 610°C were quoted - see WJ. Jackson, The British Polymer Journal, December 1980, p. 155. In order to depress the high melting point of the homopolymer so as to make it melt fabricable, a variety of materials incorporating different types of comonomers were prepared over the years.
  • One such material is, for example, the resin made from p-hydioxybenzoic acid, isophthalic and/or terephthalic acids and 4,4-biphenol as described in Corns et al., U.S. Patents Nos. 3,637,595 and 3,975,487.
  • the polymer has outstanding high temperature properties and can be molded to give articles of high modulus and strength. It is offered commercially by Amoco Performance Products, Inc. under the trade name of Xydar ® . These LCPs usually contain a relatively high percent concentration of hydroxybenzoic acid to reduce the concentration of the expensive biphenol.
  • the main drawback of the prior art p-hydroxybenzoic acid copolymers and LCP polyesters containing no p-hydroxybenzoic acid moieties is the relatively high cost associated with the use of an expensive comonomer, such as 4,4'-biphenol, substituted hydroquinones (e.g., phenylhydroquinone), naphthalene diols, naphthalene
  • an expensive comonomer such as 4,4'-biphenol, substituted hydroquinones (e.g., phenylhydroquinone), naphthalene diols, naphthalene
  • polyesters prepared from terephthalic acid, hydroquinone and varying
  • polyester preferably on the diol ring.
  • diol ring preferably on the diol ring.
  • the melting point typically the mechanical properties are also
  • polyesters forming oriented melts were made from a variety of substituted hydroquinones. See, for example, Lee et al., U.S. Patent No. 4,600,765; Hutchings et al., U.S. Patent Nos. 4,614,790 and 4,614,791; and Funakoshi et al., U.S. Patent No. 4,447,593.
  • 4,4'-dihydroxydiphenyl sulfide are the subject of Dicke et al., U.S. Patent No.
  • transition temperature is generally low and the high temperature
  • first polyester polymer comprising recurring moieties of dihydroxyarylene comprising hydroquinone, a nonvicinal benzene dicarboxylate (preferably terephthalic acid and mixtures of terephthalic acid and isophthalic acid) and p-oxybenzoate
  • second polyester polymer comprising recurring moieties of naphthalene based monomers, p-oxybenzoate, or substituted hydroquinone wherein said polymers and the moieties making up the polymers are present in specified proportions, yields alloys with improved processibi ⁇ ty, improved mechanical properties, and improved surface characteristics (such as reduced tendency to blister or better gloss). In some cases, the alloys have better properties than the individual polymers at reduced cost
  • mixtures of polymeric materials are generally immiscible. That is, they consist of domains of chemically distinct phases. Usually, one component forms a continuous phase, while the other component forms roughly spherical domains as inclusions. Under some circumstances, bi-continuous structures are also obtainable. Mixing two arbitrarily chosen polymers usually results in inferior materials having no utility, since in the absence of adhesion between phases, the dispersed phase merely weakens the continuous phase.
  • Some polymeric products, such as the wholly aromatic polyesters exhibit an ordered structure in at least some regions of the polymer. This order can exist in one, two or three dimensions.
  • the incorporation into blends of polymers exhibiting an ordered structure leads to an increased tendency of the blends to separate into phases. This is believed to be due to the fact that the order found in certain regions of the resin causes a fairly sharp boundary between the domains of the molecules of the component polymers. Hence, blends including such polymers would be expected to exhibit a significant reduction in properties.
  • Cottis U.S. Patent No. 4,563,508, is directed to the improvement of molding compounds based on wholly aromatic polyesters by the addition of a minor amount of a flow modifier wherein at least 30 mole percent of the aromatic diol is biphenol.
  • the flow modifier crystallizes poorly and improves the flow of the highly crystallized base polymer it is added to.
  • the flow modifier does not enhance the end properties of the blend -composition. It is to be noted that the addition of the flow modifier decreases the HDT of the composition and does not increase the strength.
  • Takayanagi et al. U.S. Patent No. 4,228,218, discloses a polymer composition comprising 20 percent or less, based upon the total weight of polymeric material, of a first rigid polymer with the balance being a second polymer composed substantially of flexible molecular chains.
  • the first polymeric material is dispersed in the second polymeric material in a microscopic region of 1 ⁇ m or less. It is believed that wholly aromatic polyesters would be characterized by those skilled in the art as rigid molecules within the context of the above cited patent The patent does not disclose blends of two or more polymers having rigid chains.
  • Blends of polymers exhibiting orientation in the melt with other polymers were investigated.
  • Mixtures of liquid crystalline polyesters with poly(alkylene terephthalates), polycarbonates and polyarylates were described in Cincotta et al., U.S. Patent Nos. 4,408,022 and 4,451,611; Froix, U.S. Patent Nos. 4,489,190 and 4,460,735; and in Kiss, European Patent Application No. 169,947. Improved mechanical properties were found with these materials.
  • the addition of a particular liquid crystal polymer to poly(butylene terephthalate) or other thermoplastic polymers was described as a method to obtain compositions with enhanced resistance to melt dripping during burning (see Kim et al., U.S. Patent No.
  • Liquid crystalline materials including polyesters, were used to decrease the viscosity and improve the processibility of a number of other resins, including fluorinated polyolefins (see Bailey et al., U.S. Patent No. 4,417,020; Cogswell et al., U.S. Patent Nos. 4,429,078 and 4,438,236; and George et al., U.S. Patent No. 4,650,836).
  • thermotropic 6-hydroxy-2-naphthoic acid- p-hydroxybenzoic acid c ⁇ polymer blends with nylon 6, poly(butylene terephthalate), and polycarbonate prepared by screw injection molding, was studied by Beery et al. J. Mater. Sci. Lett. 1988. 7(10), pp. 1071-3.
  • the morphology was found to be strongly dependent on the flow history and on the composition of the subject mixtures.
  • Molding compositions comprised of the above first and second polyester, filler, and optionally a polymeric flow modifier are claimed in commonly assigned U.S. Patent Application entitled “Molding Compositions Comprising Mixtures of Wholly Aromatic Polyesters and Fillers,” Serial No. 060,114 filed on June 9, 1987 in the name of J.J. Duska, hereby incorporated by reference.
  • polyesters are based on identical monomers but differ in the relative proportion of the monomers, wherein each of said polyesters has unsatisfactory molding and extrusion characteristics and obtain good molding and extrusion grade compositions.
  • advantageous alloys can be formed comprising a first LCP polyester, consisting essentially of units (I), (II), (llI), and (IV)
  • a second LCP polyester polymer comprising at least one moiety selected from the group consisting of hydroxybenzoic acid, hydroxynaphthalene carboxylic acid, dihydroxy naphthalene, naphthalene dicarboxylic acid oxybisbenzoic acid and substituted hydroquinones wherein the said moiety or moieties comprise at least about 5 mole percent of the units in said second LCP polyester.
  • the first LCP polyester useful in this invention forms a stable oriented melt phase at about 200 to about 420°C preferably from about 250 to 380°C; the melt phase is tractable and can be melt extruded with the second LCP polyester polymer to form quality, high performance fibers, films, molded objects, etc.
  • the first LCP polyester is based on relatively inexpensive monomers such as terephthalic acid, isophthalic acid, hydroquinone and hydroxybenzoic acid while the second LCP polyester comprises expensive monomers such as naphthalene diol,
  • each of the expensive monomer moieties in the second LCP polyester can impart orientation in the melt at a level of at least about 5% of the units in the polymer while biphenol is generally used with hydroxybenzoic acid or hydroxynaphthoic acid moieties. Hydroxybenzoic acid moieties also can impart orientation in the melt at a level of at least about 5% of the units of the polymer.
  • the second LCP polyester must comprise at least one moiety selected from the group consisting of hydroxybenzoic acid, hydroxynaphthalene carboxylic acid, oxybisbenzoic acid and substituted hydroquinone in a concentration sufficient to provide at least about 5 mole percent of the units in said second LCP polyester to provide orientation in the melt
  • the first polyester has a higher concentration of hydroquinone units than the second polyester.
  • the concentration of second LCP polyester can range from about 0.01 to 99 parts by weight per each part by weight of first LCP polyester, preferably .3 to 99 parts by weight and most preferably 0.3 to 3. In general, the higher the concentration of first LCP, the lower the cost of the alloy.
  • the first polyester of this invention having a melting point under 420oC and a molecular weight of about 2,000 to 200,000 consists essentially of units (I), (II), (Ill), and (lV)
  • the preferred first polyesters of this invention have melting points from about 250°C to about 380°C, p is approximately equal to q + r, q ranges from about 0.05 to about 0.7, r ranges from about 0.3 to about 0.95 and s ranges from about 0.07 to about 1.5.
  • polyesters which are the subject of application numbers (Case 29,723) and (Case 29,724) filed on even date, which are hereby incorporated by reference.
  • One class of preferred LCP polyesters useful in this invention form a stable oriented melt phase at 340 to 400°C, preferably from 340 to 380°C; the melt phase is tractable and can be melt-extruded below its decomposition temperature to form quality, high performance fibers, films, molded articles, and the like. Fabricated products of these polymers alone show high strength as well as good retention of properties at high temperatures. Materials filled with 30 percent by weight of glass fibers have heat distortion temperatures of over 240 to about 280°C and higher, under a load of
  • the crystallization temperatures of these copolymers are in the range of from 300 to 340°C preferably from 310 to 340°C; and their crystallization rates are at least 1,000 and up to 3,500 counts per minute, preferably from 1,500 to 2,000 counts per minute.
  • a second class of preferred LCP polyesters useful in this invention form a stable oriented melt phase at about 250 to 360°C, the melt phase is tractable, and the polymers display a significant improvement in moldability and can be melt-extruded below their decomposition temperatures to form quality, high performance fibers, films, molded articles, and the like. Fabricated products show good surface properties, high strength, and good retention of properties at high temperatures.
  • materials filled with 30 percent by weight of glass have heat distortion temperatures of over 200 to about 240°C and higher, under a load of 264 psi. It is believed that the higher the amount of crystallinity of the polymer the higher the heat distortion temperature (HDT) will be, also the higher the melting point
  • the instant copolyesters are prepared by charging into the reactor the required amounts of isophthalic and terephthalic acids, p-hydroxybenzoic acid and hydroquinone.
  • An anhydride of a lower monocarboxylic acid preferably an anhydride of a C 2 to C 4 monocarboxylic acid, is added in at least stoichiometric amounts. It is most preferred to use acetic anhydride; its amount is preferably from about 5 to about 20 mole percent over that required for the acetylation of all of the hydroxyl groups.
  • the acetylation reaction takes place at about 140°C for a period of time of from about 2 to about 6 hours.
  • the reaction mixture is then heated to about 240 to 320°C at a rate of about 10 to 40°C per hour, and is kept at about 240 to 320°C for approximately a few minutes to about 4 additional hours.
  • the low molecular weight polymer obtained is then solid state advanced to the required high molecular weight by heating to a temperature of from about 265 to about 340°C, for a period of time of from about one to about 24 hours.
  • a preferred variant as described in Finestone, U.S. Patent No.4,742,149 comprises adding a salt particularly an alkaline earth metal salt or an alkali metal salt preferably potassium sulfate, during the preparation of the resin and particularly to the prepolymer melt prior to advancement of the final product to the desired degree of polymerization.
  • a salt particularly an alkaline earth metal salt or an alkali metal salt preferably potassium sulfate preferably potassium sulfate
  • end groups depending upon the synthesis route selected.
  • the end groups optionally may be capped, e.g., acidic end groups may be capped with a variety of alcohols, and hydroxyl end groups may be capped with a variety of organic acids.
  • end capping units such as phenyl ester
  • the polymers can be annealed below their melting points for a period of time or the polymers may be oxidatively crosslinked to at least some degree, if desired, by heating in an oxygen-containing atmosphere (e.g., in air) while in bulk form or as a previously shaped article at a temperature below their melting points for a limited period of time (e.g., for a few minutes).
  • an oxygen-containing atmosphere e.g., in air
  • polyesters of the present invention tend to be substantially insoluble in all common polyester solvents such as hexafluoroisopropanol and o-chlorophenol, and accc-idingly are not susceptible to solution processing. They can surprisingly be readily processed by known melt processing techniques as discussed hereafter.
  • polyesters of the present invention commonly exhibit weight average molecular weights of about 2,000 to about 200,000.
  • polyesters alone can be melt processed in the substantial absence of polymer degradation to form a variety of relatively stiff shaped articles, e.g., molded three-dimensional articles, fibers, films, tapes, etc.
  • the polyesters are suitable for molding applications and may be molded via standard injection molding techniques commonly utilized when forming molded articles. Unlike the polyesters commonly encountered in the prior art it is not essential that more severe injection molding conditions (e.g., higher temperatures), compression molding, impact molding, or plasma spraying techniques be utilized. Fibers or films may be melt extruded. In some instances, as described in Cottis et al., U.S. Patent No. 4,563,508, melt fabrication may be facilitated by adding flow aids.
  • These polymers can contain up to 10 mole percent (based on total reactants) of carbonate linkages and/or aromatic comonomers other than (I)-(IV), such as biphenol, provided that the use of said carbonate linkages and/or comonomers does not unfavorably affect the very attractive properties of the instant copolyesters.
  • the first LCP polyesters are blended with a second different LCP polyester comprising at least one moiety selected from the group consisting of hydroxybenzoic acid, hydroxynaphdialene carboxylic acid, dihydroxy naphthalene, naphthalene dicarboxylic acid, oxybisbenzoic acid and substituted hydroquinones wherein the said moiety or moieties comprises at least about 5 mole percent of the units in said second LCP polyester.
  • the preferred second LCP polyesters consist essentially of one or more units H,
  • R is at least one member selected from the group consisting of naphthalene and phenyl, alkyl (t-butyl), aralkyl
  • R 1 is at least one
  • R 2 is at least one member selected from the group consisting of naphthalene and oxybiphenyl
  • R 3 is at least one member selected from the group consisting of p-phenylene and m- phenylene
  • R 4 is at least one member selected from the group consisting of phenylene, biphenylene and oxybiphenyl
  • h + j + k + 1 + m is approximately equal to l
  • h +j + k 0.05 to 1
  • h + m is approximately equal to k + 1 and from about 0.05 to 1.0 units
  • polyester (preferably at least 0.15 units) in the polyester comprise at least one member selected from the group consisting of naphthalene, phenyl, alkyl (t-butyl), aralkyl (styryl or
  • each of the phenyl and phenylene groups are preferably para and the naphthalene groups are drawn infra.
  • Suitable second LCP polyester useful in this invention include: a second polyester comprising units (IX), (X), and (XI):
  • e is approximately equal to f; e is one; and g is in the range of from about 1.5 to about 5, preferably in the range of from about 2 to about 4, based on the number of moles of monomer corresponding to units (TX); where the molecular weight of said polyester is in the range of from about 2,000 to about 200,000; said second polyesters when admixed with the first LCP yield blends tiiat are easy to melt fabricate, display vastly improved moldability and physical properties, yield parts pleasing to the eye; land, surprisingly, show a reduced tendency to blister on molding.
  • a totally unexpected and surprising feature of the instant blends is that both their moldability and the surface characteristics of the molded objects obtained from them, are often better than the corresponding properties of many of the individual polyesters.
  • the materials display improved mechanical properties over tiiose of the constituent polymers.
  • Heat distortion temperatures, bodi on neat or on 30 percent by weight glass fiber filled compositions often range from at least 200° C to as high as 350° C and higher under a load 264 psi, particularly when alloyed with preferred class 1 polyesters.
  • Another second polyester comprises unit (V), (VI), (VII), and (Vlll):
  • a is approximately equal to b + c; b is in the range of from about 0.5 to about 0.8; c is in the range of from about 0.5 to about 0.2; and d is in the range of from about 1 to about 7, preferably from about 2 to about 4, based on the total number of moles of monomer corresponding to units (V) where said polyester has molecular weights in the range of from about 2,000 to about 200,000, said second polyesters when admixed with the first LCP yield blends tiiat are easy to melt fabricate and yield injection molded parts that surprisingly show a significandy decreased tendency to blister.
  • the materials display improved mechanical properties over tiiose of the constituent polymers, as well as improved
  • composites with preferred class 1 polyester containing about 30 weight percent of glass fibers have heat distortion temperatures (HDTs) of at least 240°C, when measured under a load of 264 psi.
  • HDTs heat distortion temperatures
  • An additional second polyester polymer comprises at least 1 unit :
  • Ar comprises at least one member selected from the group consisting of:
  • X 1 and X 2 are independendy oxy or carbonyl optionally in conjunction with units:
  • the Ar group of the second polyester can also comprise a divalent radical comprising at least one phenylene group such as phenylene, biphenylene and oxybiphenyl, having molecular weight of from about 2,000 to about 200,000.
  • the instant blends with the preferred class 1 polyester are generally easier to melt fabricate, display improved moldability and yield parts pleasing to the eye with good surface characteristics.
  • the materials usually have improved mechanical properties that are quite often superior to the properties of the two constituent polymers.
  • Heat distortion temperatures, both on neat and on 30 percent by weight glass filled blend compositions are at least 175°C and may be as high as 300°C and even higher, when measured under a load of 264 psi.
  • Especially preferred second polyesters are the copolyesters which are disclosed in U.S. Patent Nos.4,161,470; 4,184,996; and 4,256,624, herein incorporated by reference.
  • the polyester disclosed in U.S. Patent No.4,161,470 is a melt processible wholly aromatic polyester which is capable of forming an anisotropic melt phase at a temperature below approximately 350°C apart from the blend.
  • the polyester consists essentially of the recurring moieties (XIX) and (XX) which may include substitution of at least some of the hydrogen atoms present upon an aromatic ring:
  • the wholly aromatic polyester there disclosed comprises approximately 10 to 90 mole percent of moiety (XlX) and approximately 90 to 10 mole percent of moiety (XX).
  • the polyester disclosed in U.S. Patent No. 4,184,996 is a melt processible wholly aromatic polyester which is capable of forming an anisotropic melt phase at a temperature below approximately 325°C apart from the blend.
  • the polyester consists essentially of the recurring moieties (XX) (XXI) and (XXll):
  • the wholly aromatic polyester there disclosed comprises approximately 30 to 70 mole percent of moiety (XX).
  • the polyester preferably comprises approximately 40 to 60 mole percent of moiety (XX); approximately 20 to 30 mole percent of moiety (XXI); and
  • the polyester disclosed in U.S. Patent No.4,256,624 is a melt processible wholly aromatic polyester capable of forming an anisotropic melt phase at a temperature below approximately 400°C apart from me blend.
  • the polyester consists essentially of the recurring moieties (XIX), (XXlll) and (XXlV) which may include substitution of at least some of the hydrogen atoms present upon an aromatic ring:
  • the polyester comprises approximately 10 to 90 mole percent of moiety (XIX), approximately 5 to 45 mole percent of moiety (XXllI), and approximately 5 to 45 mole percent of moiety (XXIV).
  • any of the LCP polyesters based on substituted hydroquinones discussed above can be used as the second LCP polyester such as poly phenyl substituted phenylene terephtiialates of U.S. Patent No. 4,159,365.
  • the phenomenon of blistering is known. Blisters may occur near a surface or in the bulk of the sample.
  • blistering occurs especially between two layers of different composition.
  • blistering is known to be a localized delamination at an interface; it depends on the diffusion of chemicals such as water and degradation by-products.
  • the difference in the thermal expansion coefficient between a coating and the substrate can create stresses and may weaken the interface.
  • a blister may then form with less pressure difference, due to volatiles, than in cases where these stresses are absent
  • blistering is due to a surface layer delamination and can be caused eitiier by trapped volatiles or by built-in stresses. Most probably bodi factors are at work.
  • Blisters which occur during molding generally indicate the presence of degraded material. Quite often parts having acceptable surface characteristics are obtained upon molding. However, when tiiese parts are treated at high temperatures for a certain period of time, blisters ("oven blisters") often appear. These do not necessarily indicate the presence of degraded material as a result of molding.
  • blends of the instant invention show a considerably decreased tendency to blister- both during molding and in the oven test
  • Molding compounds may be formed from the subject copolyesters and blends by incorporating therein fillers such as talc, wollastonite or titanium dioxide; and/or reinforcing agents, e.g., glass fibers.
  • fillers such as talc, wollastonite or titanium dioxide
  • reinforcing agents e.g., glass fibers.
  • One attractive application of the novel copolyesters of the instant invention is, for example, in ovenware. Both the neat polymers or composites as disclosed by Duska et al., U.S. Patent No.4,626,557 are useful in this application. Molding compounds of interest in ovenware are described in commonly assigned U.S. Patent application entided "Novel Plastic Ovenware Compositions," Serial No. 255,753. Articles may also be molded from a molding compound which includes, as one component, the blend of the present invention.
  • Such a molding compound incorporates into the blend of the present invention approximately 1 to 80 percent preferably approximately 10 to 70 percent by weight based upon the total weight of the molding compound, of a solid filler and/or reinforcing agent
  • Representative fibers which may serve as reinforcing media include glass fibers, asbestos, graphitic carbon fibers, amorphous carbon fibers, synthetic polymeric fibers, aluminum fibers, aluminum silicate fibers, oxide of aluminum fibers, titanium fibers, magnesium fibers, rock wool fibers, steel fibers, tungsten fibers, etc.
  • Representative filler materials include calcium silicate, silica, clays, talc, mica, carbon black, titanium dioxide, wollastonite, polytetrafluoroethylene, graphite, alumina trihydrate, sodium aluminum carbonate, barium ferrite, etc.
  • the molding compounds are useful in a variety of applications including high temperature applications, for example, in cookware and electrical articles, and the like.
  • talcs which are of high purity, are selectively
  • the weight loss on ignition of the suitable talcs is not more tiian 6 percent or less at 950°C and is 2 percent or less at 800°C.
  • the iron content analyzed as iron oxide (Fe 2 O 3 ) will not be more dian about 1 percent and tiiat of the particularly preferred talcs will not be more than about 0.6 percent and may be less.
  • the particle size distribution of the talc must preferably be such that about 90 to 95 percent of the particles are less than about 40 microns.
  • talcs containing the minimum amounts of decomposable material will be presented in amounts of from about 1 percent to about 60 percent based on the total composition weight with the preferred range being from about 35 percent to about 55 percent
  • Rutile titanium dioxide can also be employed in conjunction with the talc material, including mixtures of highly refined talcs and otiier talc.
  • the rutile titanium dioxide will be present in a proportion of from about 2 percent to about 20 percent based on the weight of the total composition. The preferred range is from about 2 percent to about 15 percent
  • the resins will generally comprise from about 35 percent to about 85 percent and the total inerts from about 65 percent to about 15 percent
  • the inerts will comprise from about 40 percent to about 55 percent of the molding compositions.
  • the inerts will comprise up to about 55 percent of highly refined talc and from about 0 to about 10 percent of titanium dioxide.
  • compositions of the present invention can be prepared by extrusion in accordance with generally known practice.
  • a twin screw extruder can be employed with addition of the polymer, selected talc, and titanium dioxide at the feed throat and with addition of the glass roving at both the vent and feed throat.
  • compositions so prepared can then be injection molded according to general practice using techniques familiar to the injection molding field.
  • X-ray diffraction data were obtained using a Philips XRG-3000 X-ray generator equipped with a vertical diffractometer, a long, fine focus copper X-ray tube, a Paar HTK-10 high temperature diffractometer attachment and a Paar HTK-heat controller. Diffractometer position is controlled by computer, which also measures and records radiation count rate produced by sample crystallinity and sample temperature.
  • a sample of the polymer is submitted to a preliminary X-ray diffraction scan between 15 and 25 degrees two-theta angle by increasing the temperature by increments of 60°C within a temperature range from about 200 to about 480°C. This allows determination of the approximate temperature at which the peak located at approximately 19.7 degrees two-theta (4.50 A d-spacing) reaches its minimum value, i.e., an approximate melting point
  • a second-degree polynomial equation is derived from the above data; this polynomial equation now allows to follow the peak angle as the sample temperature is varied.
  • the temperature at which the peak height reaches a minimum is considered to be the melting point
  • the polymer sample is now heated and cooled at a rate of 100°C per minute between the previously mentioned temperature limits, and its melting point is determined Since the melting point of a crystalline material often changes on heating and cooling (due to recrystallization, further polymerization, etc.), the sample is cooled and reheated. This allows determination of the melting point on the second heating cycle. Generally, the second cycle yields a melting point which remains approximately constant if additional heating or cooling cycles are performed. Therefore, the value obtained in the second heating cycle is taken as the polymer melting point.
  • the crystalline melting point is measured by following the intensity of the X-ray diffraction of the most intensive peak as a function of
  • the intensity of X-ray diffraction of a crystalline material can be expressed as counts per second (or any unit of time).
  • the increase in the number of counts per unit of time while the sample is being cooled at a certain rate (100°C per minute) is therefore proportional to the rate of crystallization.
  • a temperature interval starting at the onset of crystallization and 40°C below tiiat temperature was arbitrarily chosen. Rates of crystallization are expressed as the increase in counts per minute for a sample cooled within these temperature limits during the second cooling cycle.
  • the measurement is performed using a Dupont Dynamic Mechanical Analyzer (DMA), Model 982 in conjunction with a thermal analyzer, Model 1090.
  • DMA Dupont Dynamic Mechanical Analyzer
  • the DMA measures changes in the viscoelastic properties of materials as a function of time and temperature. Tests are conducted at a heating rate of 5°C per minute. When the run is complete, the stored data is analyzed; the storage modulus (very similar to the flexural modulus) and the loss modulus are calculated and plotted as a function of temperature. The modulus is expressed in GPa's and the temperature in degrees Centigrade. Conversion into psi's is performed using the equation:
  • Modulus (psi) Modulus (GPa) x (1.45*10 5 )
  • CF Compressive Flow
  • CF is measured from the area of a disc obtained from a sample of powdered material of given weight usually 0.5 to 1.0 grams which has been pressed between two parallel plates.
  • a sample is pressed between two sheets of aluminum foil which in turn are backed by chromium-plated steel plates 6" x 6" x 1/4".
  • a Carver 2112-X Model No. 150-C hydraulic press modified for 800°F is used to press the sample. The particular temperature of the press is that indicated in each sample run.
  • the sample material is allowed to stand for 5 minutes between the plates at holding pressure in order that the temperature of the material can equilibrate with the press temperature.
  • a load of 5,000 pounds is then applied for 2 minutes.
  • the CF is then calculated on the following basis.
  • the area of the pressed molding compound is measured by cutting an aluminum sandwich out of the sample pressed between the two aluminum foil sheets.
  • the aluminum foil has a known area/weight relationship called the foil factor.
  • the area is normalized for the pressure of the applied load and tiiat number is multiplied by 100 to give a number greater than 1.
  • the compressive flow is tiien calculated by means of the following equation:
  • Test sample lot normally includes five tensile bars (1/8" thick), five HDT bars (5" x 1/2" x 1/4" thick) and five flex bars
  • the numerical blister rating is calculated using the equation:
  • the individual ratings for the entire set of test samples are generally treated as a single population.
  • the ratings vary widiin the range of 0 (no blistering) to 16 (severe blistering, worst case).
  • Fiber ratings were obtained using a hot bar apparatus with a temperature range from 270 to 415°C.
  • a 2 to 5 gram sample of polymer is thinly and evenly sprinkled on the upper portion of the hot bar using a spatula and is allowed to melt Using a large pair of tweezers, grab a small portion of material from the melted pool and slowly draw a fiber at a steady speed.
  • the following rating system is used: 0 - Material does not melt or does not draw a fiber
  • VPS or vapor phase soldering is an assembly technique used to solder components to a printed circuit board. This technique involves heating a fluid to its boiling point so that a vapor is produced tiiat is above the melting temperature of standard solder. The printed circuit assembly is placed into the vapor blanket The vapor condenses onto the printed circuit assembly and causes the solder to reflow.
  • the vapor phase unit used was Model No.912 II manufactured by HTC.
  • the primary vapor was FC-70 Fluorinert an inert fluorochemical manufactured by 3M Company.
  • the vapor was at a temperature of 428°F (220°C).
  • the secondary vapor was Genesolv D, a trichlortriflu ⁇ roethane manufactured by Allied Chemical Company. The vapor was maintained at a temperature of approximately 117°F (47°C).
  • Items A through F were charged to a 15-gallon, oil heated vessel equipped with an anchor type stirrer, reflux condenser, after condenser, injection port and distillate receiver. After purging widi nitrogen, the contents were heated with stirring to 141°C and held under reflux at that temperature for 3 hours. Distillation was then started while increasing the temperature over a 4.8 hour period to 285°C. Item G was tiien injected into the vessel. After an additional 15 minutes the contents of the vessel were transferred to a sigma blade mixer that had been preheated to 320°C. After mixing for 4 hours at this temperature under an atmosphere of nitrogen, the mixer was cooled to near room temperature where the contents were removed as a granular solid.
  • the melting point of the polymer (X-ray) was 359°C; its crystallization temperature was 336°C with a crystallization rate of 2,400.
  • a sample of the polymer was melted, extruded and pelletized with a twin screw extruder.
  • the pellets were molded into test specimens.
  • the resulting testing showed superior high temperature performance with a heat distortion temperature of 250°C and a flexural modulus of 570,000 psi as measured at 250°C by DMA.
  • a molding composition containing 70 weight percent of the above polymer and 30 weight percent of milled glass fiber was prepared by compounding on a twin screw extruder and molded into test specimens.
  • the heat distortion temperature of the obtained composite was 264°C and its flexural modulus (by DMA) was 520,000 psi as measured at 250°C. (ASTM-D-4065)
  • Example P-1 The ingredients were the same as in Example P-1 with the exception that the amount of item F was 14.16 grams, and tiiat item G was not used in the preparation.
  • the equipment was the same as in example 1 and the operating procedure is described below.
  • the contents of the vessel were transferred to a sigma blade mixer which had been preheated to about 250°C.
  • the material was mixed while the temperature was increased to 300°C and mixing was continued for a total of 5 hours at that temperature.
  • a molding composition containing 70 weight percent of the above polymer and 30 weight percent of milled glass fiber was prepared by compounding on a twin screw extruder and molded into test specimens.
  • the heat distortion temperature of the obtained composite was 250°C and its flexural modulus (by DMA) was 420,000 psi as measured at 250°C. (ASTM-D-4065)
  • Example P-2 The ingredients were the same as in Example P-2 with the exception of item F the amount of which was 7.08 grams; also, 16.00 grams of triphenyl phosphite were added prior to transfer of the reaction mixture to the sigma blade mixer. Otherwise, the procedure was the same as in Example P-2.
  • the melting point of the polymer (X-ray) was 359°C; its crystallization temperature was 329°C with a crystallization rate of 2,500.
  • a molding composition containing 70 weight percent of the above polymer and 30 weight percent of milled glass fiber was prepared by compounding on a twin screw extruder and molded into test specimens.
  • the heat distortion temperature of the obtained composite was 268°C and its flexural modulus (by DMA) was 480,000 psi as measured at 250°C. (ASTM-D-4065)
  • the melting point of the polymer (X-ray) was 353°C; its crystallization temperature was 331°C with a crystallization rate of 2,100.
  • a molding composition containing 70 weight percent of the above polymer and 30 weight percent of milled glass fiber was prepared by compounding on a twin screw extruder and molded into test specimens.
  • the heat distortion temperature of the obtained composite was 240°C.
  • Triphenyl phosphite 16.00 g Items A through F were charged to a 15-gallon, oil heated vessel equipped with an anchor type stirrer, reflux condenser, after condenser, injection port, and distillate receiver. After purging with nitrogen, the contents were heated witii stirring to 141°C and held under reflux at that temperature for 3 hours. Distillation was then started while increasing the temperature 20°C/hr to 259°C. Item G was then injected into the vessel. After the reactor reached 263°C the contents of the vessel were transferred to a sigma blade mixer that had been preheated to 300°C. After mixing for 5 hours at this temperature under an atmosphere of nitrogen, the mixer was cooled to near room temperature where the contents were removed as a granular solid.
  • the melting point of the polymer (X-ray) was 268°C; its crystallization temperature was 248°C with a crystallization rate of 186.
  • a sample of the polymer was blended with glass, melted, extruded and pelletized with a twin screw extruder. The pellets were molded into test specimens. The resulting testing showed superior high temperature performance with a heat distortion temperature of 238°C.
  • Example P-7 This example describes the preparation of a polyester in the laboratory. It is to be noted tiiat the preferred method is described in Example P-7 and the following wherein the polymers were produced in scaled-up size in the pilot plant There a continuous method of in situ polymerization was utilized which is more demonstrative of scale-up production and economies. Unfortunately in scale-up production, physical and mechanical operating parameters can be varied as compared to laboratory production.
  • the polyester had the molar composition: terephthalic acid/isophthalic acid/p-hydroxybenzoic acid/hydroquinone 0.5/0.5/1.0/1.0 (see Cottis et al., U.S. Patent No. 3,637,595; example no. 10, noted as designation"x" on Figure 1).
  • the above mixture was heated at reflux for a period of 3 hours; vigorous stirring was maintained diroughout the reaction. At the end of the reflux period collection of distillate was started. The reaction mass was then heated at a rate of about 30°C per hour to 311°C at which point 98.2 percent of the theoretical distillate was collected.
  • the molten material was poured into an aluminum pan and allowed to cool to room temperature. The solid was pulverized and ground to pass a 2 millimeter screen. The powder was placed in a drum and was heated in a nitrogen stream, while rotating, to a temperature of 330°C; and held at tiiat temperature for two hours. The product was removed from the drum after cooling.
  • the melting point of the polymer was 325°C; its crystallization temperature (onset of crystallization) and crystallization rate (both measured via X-ray techniques) were 299°C and 2,242, respectively.
  • the neat polymer had a HDT of 226°C, a flex strength of 16,000 psi, a flex modulus of 1.85 X 10 6 psi and a blister rating of 16.
  • This example describes the preparation of a polyester having the mole ratio of 0.5/0.5/1.0/1.015. The following ingredients were combined in the manner described:
  • polyester having the following molar composition: 0.25 moles isophdialic acid/0.75 moles terephdialic acid/3.0 moles p-hydroxybenzoic
  • polyester having the following molar composition: 1 mole terephthalic acid/3.7 moles p-hydroxybenzoic acid/1 mole 4,4-biphenol.
  • Items A through E were charged into the rector and heated to 307°C over a period of 10 hours with distillation of acetic acid.
  • Item F was men added and heating was continued for 6 minutes to a melt temperature of 310°C.
  • the contents of the vessel were transferred to a sigma blade mixer that had been preheated to 335°C. The temperature was raised to 350°C and mixing was continued at 350°C for 9.5 hours under an atmosphere of nitrogen. The mixer was cooled to near room temperature where the contents were removed as a granular solid having a compressive flow of 52.
  • naphthalene-based polyester used in the instant blends was Vectra ® A950, produced by the Hoechst-Celanese Corporation and composed of about 73 molepercent 4-oxybenzoyl moieties (XX) and 27 mole percent of 6-oxy-2-naphthoyl moieties (XlX):
  • Polyesters prepared as described in preparative examples 1 and 2 were formulated into a 30 percent glass filled composition, compounded and pelletized.
  • the blends contained as a percentage of the resins phase, either 0, 10, 21 or 40 weight percent of polymer (b).
  • the formulations were compounded and pelletized on a 25 mm diameter Berstorff twin screw extruder.
  • the barrel profile temperature for compounding was:
  • Barrel zone 1 320 to 325°C
  • Barrel zone 3 355 to 376°C
  • Barrel zone 4 365 to 395°C
  • Barrel zone 5 380 to 400oC
  • Barrel zone 6 370 to 380°C
  • Barrel zone 7 360 to 370°C
  • the screw rpm was 170 to 175; the output was 12 to 15 pounds per hour.
  • the above materials were molded on a 75 ton, 3 ounce Newbury injection molding machine.
  • the barrel profile was:
  • the mold temperature was set at 121°C and the injection pressure was in the range of 1,000 to 1,360 psi.
  • the molding machine screw rpm was about 330.
  • Barrel zone 1 293 to 320°C
  • Barrel zone 3 375 to 400°C
  • Barrel zone 6 370 to 385°C
  • Barrel zone 7 375 to 387°C
  • the screw rpm was 175 with an output of about 10 to 13 pounds per hour.
  • the mold temperature was set at 120°C for composition no.7 and at 66°C for all other compositions.
  • the injection pressure was 1,000 psi and the molding machine screw rpm was about 330.
  • Barrel zone 1 150 to 176°C
  • Barrel zone 2 270 to 345°C
  • Barrel zone 3 285 to 365°C
  • Barrel zone 4 275 to 370°C
  • Barrel zone 5 270 to 370°C
  • Barrel zone 6 280 to 365°C
  • Barrel zone 7 275 to 360°C
  • Barrel zone 1 185 to 301°C
  • Barrel zone 2 370 to 385°C
  • Barrel zone 7 370 to 376°C
  • Barrel zone 1 320°C
  • Barrel zone 3 370 to 375°C
  • Barrel zone 7 370 to 376°C
  • the screw rpm was in the range of 120 to 175 for all the blends; the output was about 10 to 13 pounds per hour.
  • Front zone 271 to 337°C
  • Front zone 332 to 382°C
  • Front zone 288 to 377°C
  • the mold temperature was set at 66°C for compositions 21 to 32 and 36; it was 99°C for no 44 and 120°C in all other examples.
  • the injection pressure was:
  • the molding machine screw rpm was set at 330.
  • Table I lists the polyesters useful in this invention which by themselves have desirable properties.
  • Table ll lists borderline resins.
  • Table llI lists polymers whose properties are relatively poor.
  • Runs 1 to 26 in Table IV do not correspond to same run numbers in Tables I, ll, and llI.
  • Runs 1 to 79 in Table V do not correspond to the same number runs in Tables I,ll, lll, and IV.
  • the blends have lower injection molding temperatures than the base polymer showing they can be fabricated at lower temperatures.
  • the data clearly show that the blends display improved mechanical properties - see, for example, Table Vll flexural strengdis, test nos. 3 through 6.
  • Overall, a significant and unexpected improvement in surface properties (blister rating) is also observed.
  • the high HDTs of the novel blends are noteworthy, they are intermediate between tiiose of the constituent polymers of the blends. This in turn could be interpreted as a result of compatibility for the instant highly crystalline polyesters.
  • DMA modulus data show that stiffness is maintained up to quite high temperatures, making the present materials useful at elevated temperatures. In conclusion, therefore, the blends of this invention possess a combination of toughness, surface, and high temperature properties that could not be anticipated beforehand.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

On décrit un mélange comprenant un premier polymère polyester de cristal liquide se composant des unités (I), (II), (III) et (IV), dont le point de fusion se trouve environ en-dessous de 420°C, où p est approximativement égal à r+q, où r varie entre environ 0,05 et environ 0,09, où 9 varie entre environ 0,95 et environ 0,1 et s entre environ 0,05 et environ 9; un deuxième polymère polyester de cristal liquide comprenant au moins une partie choisie parmi le groupe se composant d'acide hydroxybenzoïque, d'acide carboxylique hydroxynaphtalène, de naphtalène dihydroxy, d'acide dicarboxylique naphtalène, d'acide oxybisbenzoïque et hydroquinones à substitution, où la ou les parties comprennent au moins environ 5 moles pour cent des unités, dans ledit deuxième polyestère de cristal liquide.
EP19890911917 1988-10-11 1989-10-10 Blends of liquid crystalline polymers of hydroquinone poly(iso-terephthalates) p-hydroxybenzoic acid polymers and another lcp containing oxybisbenzene and naphthalene derivatives Withdrawn EP0390908A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25563288A 1988-10-11 1988-10-11
US255632 1988-10-11

Publications (2)

Publication Number Publication Date
EP0390908A1 true EP0390908A1 (fr) 1990-10-10
EP0390908A4 EP0390908A4 (en) 1992-07-08

Family

ID=22969206

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890911917 Withdrawn EP0390908A4 (en) 1988-10-11 1989-10-10 Blends of liquid crystalline polymers of hydroquinone poly(iso-terephthalates) p-hydroxybenzoic acid polymers and another lcp containing oxybisbenzene and naphthalene derivatives

Country Status (5)

Country Link
US (1) US5216092A (fr)
EP (1) EP0390908A4 (fr)
JP (1) JPH03501748A (fr)
KR (1) KR900701932A (fr)
WO (1) WO1990004002A1 (fr)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5070157A (en) * 1990-08-16 1991-12-03 University Of Akron Self reinforced composite of thermotropic liquid crystal polymers
GB2285936B (en) * 1994-01-28 1997-10-15 Derek Alfred Woodhouse Treatment of fluids
AU1524897A (en) * 1996-01-05 1997-08-01 E.I. Du Pont De Nemours And Company Liquid crystalline polymer composition
TW450985B (en) * 1996-06-18 2001-08-21 Sumitomo Chemical Co Thermoplastic resin composition and its molded article
JP3387766B2 (ja) * 1997-02-03 2003-03-17 住友化学工業株式会社 液晶ポリエステル樹脂組成物
US6120854A (en) * 1999-02-19 2000-09-19 Northrop Grumman Liquid crystal polymer coating process
TW538094B (en) * 2000-04-20 2003-06-21 Ueno Seiyaku Oyo Kenkyujo Kk Liquid crystal polyester resin composition
AU2002227246A1 (en) * 2000-12-14 2002-06-24 World Properties Inc. Liquid crystalline polymer bond plies and circuits formed therefrom
US7128804B2 (en) 2000-12-29 2006-10-31 Lam Research Corporation Corrosion resistant component of semiconductor processing equipment and method of manufacture thereof
JP4798856B2 (ja) * 2001-02-23 2011-10-19 上野製薬株式会社 流動性が改良された全芳香族耐熱液晶ポリエステル樹脂組成物
JP2005539382A (ja) * 2002-09-16 2005-12-22 ワールド・プロパティーズ・インコーポレイテッド 液晶ポリマ複合物、その製造方法、およびそれから形成された物品
US7354887B2 (en) * 2002-12-18 2008-04-08 E. I. Du Pont De Nemours And Company High temperature LCP for wear resistance
US7180172B2 (en) 2003-06-19 2007-02-20 World Properties, Inc. Circuits, multi-layer circuits, and methods of manufacture thereof
US7578950B2 (en) * 2003-07-01 2009-08-25 E. I. Du Pont De Nemours And Company Liquid crystalline polymer composition
US8697817B2 (en) * 2003-09-04 2014-04-15 Ticona Llc Manufacturing process for liquid crystalline polymer
US7549220B2 (en) * 2003-12-17 2009-06-23 World Properties, Inc. Method for making a multilayer circuit
WO2005072031A2 (fr) * 2004-01-20 2005-08-04 World Properties, Inc. Materiaux pour circuits, circuits, circuits multicouches, et procedes de fabrication correspondants
US7524388B2 (en) * 2005-05-10 2009-04-28 World Properties, Inc. Composites, method of manufacture thereof, and articles formed therefrom
US7147634B2 (en) 2005-05-12 2006-12-12 Orion Industries, Ltd. Electrosurgical electrode and method of manufacturing same
US8814861B2 (en) 2005-05-12 2014-08-26 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
CN101089042A (zh) * 2006-06-15 2007-12-19 住友化学株式会社 液晶聚合物组合物及其应用
US9056950B2 (en) 2010-07-23 2015-06-16 Ticona Gmbh Composite polymeric articles formed from extruded sheets containing a liquid crystal polymer
WO2012090407A1 (fr) 2010-12-27 2012-07-05 東レ株式会社 Polyester à cristaux liquides, totalement aromatique, et son procédé de fabrication
JP5914927B2 (ja) * 2011-11-21 2016-05-11 住友化学株式会社 繊維製造用材料および繊維
JP6088620B2 (ja) * 2015-10-19 2017-03-01 住友化学株式会社 繊維製造用材料および繊維

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0102160A1 (fr) * 1982-07-26 1984-03-07 Celanese Corporation Polyester anisotrope transformable par fusion à teneur faible en groupes 6-oxy-2-naphtoyles
EP0134956A1 (fr) * 1983-07-16 1985-03-27 Bayer Ag Polyesters aromatiques thermotropes à haute rigidité et résilience; procédé pour leur fabrication et leur utilisation pour la fabrication d'objets moulés, de filaments, de fibres et de feuilles
EP0242987A2 (fr) * 1986-03-24 1987-10-28 Polyplastics Co. Ltd. Composition résineuse à propriétés anisotropiques à l'état fondu
EP0258732A2 (fr) * 1986-08-28 1988-03-09 BASF Aktiengesellschaft Résines renforcées par des fibres

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4414365A (en) * 1981-03-16 1983-11-08 Sumitomo Chemical Company, Limited Process for producing an aromatic polyester composition
US4563508A (en) * 1984-05-18 1986-01-07 Dart Industries, Inc. Injection moldable aromatic polyesters compositions and method of preparation
US5091464A (en) * 1989-12-15 1992-02-25 Amoco Corporation Polymer compositions having improved molding characteristics

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0102160A1 (fr) * 1982-07-26 1984-03-07 Celanese Corporation Polyester anisotrope transformable par fusion à teneur faible en groupes 6-oxy-2-naphtoyles
EP0134956A1 (fr) * 1983-07-16 1985-03-27 Bayer Ag Polyesters aromatiques thermotropes à haute rigidité et résilience; procédé pour leur fabrication et leur utilisation pour la fabrication d'objets moulés, de filaments, de fibres et de feuilles
EP0242987A2 (fr) * 1986-03-24 1987-10-28 Polyplastics Co. Ltd. Composition résineuse à propriétés anisotropiques à l'état fondu
EP0258732A2 (fr) * 1986-08-28 1988-03-09 BASF Aktiengesellschaft Résines renforcées par des fibres

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9004002A1 *

Also Published As

Publication number Publication date
US5216092A (en) 1993-06-01
JPH03501748A (ja) 1991-04-18
KR900701932A (ko) 1990-12-05
WO1990004002A1 (fr) 1990-04-19
EP0390908A4 (en) 1992-07-08

Similar Documents

Publication Publication Date Title
US5216092A (en) Blends of liquid crystalline polymers of hydroquinone poly(isoterephthalates) p-hydroxybenzoic acid polymers and another LCP containing oxybisbenzene and naphthalene derivatives
US5079289A (en) High modulus, high strength melt-processible polyester of hydroquinone poly (iso-terephthalates) containing residues of a p-hydroxybenzoic acid
US5147967A (en) High strength polymer of hydroquinone poly(iso-terephthalate) containing residues of p-hydroxybenzoic acid
US4983713A (en) Polyester resin exhibiting optical anisotropy in molten state containing minor amounts of 6-oxy-2-naphthoyl units
US5089594A (en) Wholly aromatic polyester of isophthalic acid, terephthalic acid, p-hydroxybenzoic acid, hydroquinone and an arylene diol
US5296542A (en) Heat resistant polymers and blends of hydroquinone poly (isoterephthalates) containing residues of p-hydroxybenzoic acid
US5066767A (en) Wholly aromatic polyesters comprising isophthalic acid, terephthalic acid, p-hydroxybenzoic acid, hydroquinone and an arylene diol
EP0020693B1 (fr) Copolyesters de terephtalate de polybutylene
US5216091A (en) High strength polymers and blends of hydroquinone poly(iso-terephthalates) containing residues of p-hydroxybenzoic acid
EP0220041A1 (fr) Copolyester
EP0395750B1 (fr) POLYMERES THERMORESISTANTS ET MELANGES DE POLY(ISOTEREPHTALATES)D'HYDROQUINONES CONTENANT DES RESIDUS D'ACIDE p-HYDROXYBENZO QUE
US5391689A (en) Aromatic polyester and polyester resin composition
CA1331900C (fr) Matiere plastique de formule particuliere et articles fabriques avec cette matiere
US5204417A (en) High strength polymers and blends of hydroquinone poly(iso-terephthalates) containing residues of p-hydroxybenzoic acid
KR920002774B1 (ko) 공중합 폴리에스테르의 제조방법
EP0390915B1 (fr) POLYESTERS ENTIEREMENT AROMATIQUES A BASE D'ACIDE ISOPHTALIQUE, D'ACIDE TEREPHTALIQUE, D'ACIDES p-HYDROXYBENZOIQUE, D'HYDROQUINONE ET DE DIOL ARYLENE
US5097001A (en) Hydroquinone poly(iso-terephthalates) containing residues of p-hydroxybenzoic acid
JP3500279B2 (ja) ポリエステル樹脂組成物及びその成形品
US5132336A (en) Plastic ovenware compositions
US5091464A (en) Polymer compositions having improved molding characteristics
US5393848A (en) Process for forming improved liquid crystalline polymer blends
KR960002954B1 (ko) 용융 이방성을 나타내는 폴리에스테르
JP2699465B2 (ja) 成形品
CA2000485A1 (fr) Melanges de polymeres cristallises liquides a base d'hydroquinone poly(iso-terephtalates) poly(acide p-hydroxybenzoique); autre lcp renfermant des derives d'oxybisbenzene et de naphtalene
JP2570708B2 (ja) 流動性の良好な耐熱性芳香族ポリエステル

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19900510

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

A4 Supplementary search report drawn up and despatched

Effective date: 19920521

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19940314

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19940927